CN103717719B - Comprise the lubricating composition of poly-(iso-butylene)/poly-(vinyl-arene) segmented copolymer - Google Patents
Comprise the lubricating composition of poly-(iso-butylene)/poly-(vinyl-arene) segmented copolymer Download PDFInfo
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- CN103717719B CN103717719B CN201280036305.7A CN201280036305A CN103717719B CN 103717719 B CN103717719 B CN 103717719B CN 201280036305 A CN201280036305 A CN 201280036305A CN 103717719 B CN103717719 B CN 103717719B
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- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 36
- 229920001577 copolymer Polymers 0.000 title claims abstract description 35
- 239000000314 lubricant Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims description 26
- 150000001993 dienes Chemical class 0.000 claims description 12
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 9
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000010552 living cationic polymerization reaction Methods 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 4
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000005266 diarylamine group Chemical group 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
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- 239000011701 zinc Substances 0.000 description 3
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- 241000219495 Betulaceae Species 0.000 description 2
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- 125000002252 acyl group Chemical group 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/10—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aromatic monomer, e.g. styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/135—Steam engines or turbines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol fueled engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/255—Gasoline engines
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
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- C10N2040/26—Two-strokes or two-cycle engines
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/02—Reduction, e.g. hydrogenation
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Abstract
The present invention provides a kind of lubricating composition, described lubricating composition comprises the oil with lubricant viscosity and poly-(alkene) embedding section as poly-(iso-butylene) (PIB) with poly-(vinyl-arene) embedding section as gathered the segmented copolymer of (vinylbenzene), and wherein multipolymer is optionally functionalised or grafting. The present invention further provides the sedimental method used in this segmented copolymer control lubricating oil composition.
Description
Invention field
The present invention relates to lubricating composition, particularly comprise the oil with lubricant viscosity and there is the lubricating composition of poly-(alkene) embedding section with the segmented copolymer of poly-(vinyl-arene) embedding section.
Background of invention
Polymkeric substance is known as the purposes of viscosity modifier or dispersant viscosity modifiers (also referred to as VM) having in the oil of lubricant viscosity. Envrionment temperature can be had the viscosity modified of reaction to provide desired level by good VM. The VM that difference performs can cause such as the undesirable raising of viscosity at low temperatures and/or effect undesirable when factoring. Such as, at high temperature, such as, in piston barrel find those under, the invalid degraded of viscosity modifier can cause degradation product burning and cylinder in carbon formed. Away from high temperature, invalid degraded can cause the oxidation of viscosity modifier, causes undesirable viscosity to improve.
Particularly for olefin copolymer viscosity modifiers, such as ethylene-propylene copolymer (OCP), usually observes limited cleanliness factor in engine piston settling. Although OCP provides good low-temperature performance, but OCP has tendency to oxidize, and at high temperature degrades invalidly.
Contrary with OCP, poly-(vinyl-arene) polymkeric substance (PVA polymkeric substance), such as, gather (vinylbenzene) and much effectively degrade, but be that oil is insoluble. Oil soluble such as, by giving PVA polymkeric substance with diene such as divinyl copolymerization, vinylbenzene. In fact, have studied styrene-butadiene-copolymer as viscosity modifier or dispersant viscosity modifiers, show the improvement of piston deposit aspect compared with main line ethylene-propylene copolymer. Such as, the open No.2010/0152082 of the U.S. discloses the styrene-butadiene block copolymer produced by anionoid polymerization. But, diene can not effectively be degraded, and needs such as by adding carbonyl side base and functionalized.
Known poly-(iso-butylene) (PIB) can not be oxidized and at high temperature can effectively degrade. But, PIB does not have good thickening properties and shows the low-temperature performance gone on business.
The multipolymer of VM can be used as and at least one item in acceptable low-temperature performance and/or degree of cleaning can be provided and the multipolymer that can simply prepare is desirable.
Invention general introduction
Find now that vinyl-arene provides good VM performance and superior degradation property such as the multipolymer of vinylbenzene and iso-butylene. Thus, poly-(vinyl-arene) that the present invention is provided in lubricating composition-poly-(iso-butylene) (PVA-PIB) segmented copolymer, such as poly-(vinylbenzene)-poly-(iso-butylene) (PS-PIB).
In one embodiment, providing package of the present invention is containing the lubricating composition of the oil and PVA-PIB segmented copolymer with lubricant viscosity. PVA-PIB segmented copolymer can be or not be tapered block copolymer, and being made up of embedding section of at least one PIB (embedding section of A) and at least one PVA embedding section (B block), wherein the mol ratio of embedding section of A/ (embedding section of A+B) is 0.5-0.97. In one embodiment, the PVA of B block can be poly-(vinylbenzene) (PS). As used herein, phrase " mol ratio of embedding section of A/ (embedding section of A+B) " means the ratio of mole number divided by the repeating unit sum in (embedding section of A+ B block) of the repeating unit in embedding section of A. Repeating unit refers to the monomer derived units in polymkeric substance.
In one embodiment, the present invention provides the lubricating composition of oil, as disclosed herein PVA-PIB multipolymer and at least one additive with lubricant viscosity, and described additive comprises dispersion agent, antioxidant, anti-wear agent, friction improver or its mixture.
In one embodiment, lubricating composition comprises oil, as disclosed herein PS-PIB multipolymer and the dispersion agent or its mixture with lubricant viscosity.
In one embodiment, lubricating composition comprises oil, as disclosed herein PVA-PIB multipolymer and the antioxidant or its mixture with lubricant viscosity.
In one embodiment, lubricating composition comprises oil, as disclosed herein PVA-PIB multipolymer and the anti-wear agent or its mixture with lubricant viscosity.
In one embodiment, lubricating composition comprises oil, as disclosed herein PVA-PIB multipolymer and the friction improver or its mixture with lubricant viscosity.
In one embodiment, combustion motor, lubricant compositions as described herein have reducing amount sulphur, p and s acid salt ash at least one.
In one embodiment, the present invention provides lubricating composition for the purposes in the engine oil of 2 strokes or 4 stroke IC engines, gear oil, automatic transmission fluid, hydraulic fluid, turbine oil, metal working fluids or turning oil.
Detailed Description Of The Invention
The segmented copolymer of the PVA polymkeric substance that the present invention is provided in lubricating composition and PIB. Present copolymer comprises embedding section " A " of PIB and embedding section " B " of PVA.
Although B block PVA can select based on the requirement of embody rule, in one embodiment, the PVA of B block can comprise styrene monomer. Vinylbenzene such as alpha-methyl styrene, α-ethyl styrene, p-t-butyl styrene and p-lower alkoxy vinylbenzene that PVA also can be replaced such as vinyl toluene, alpha-halo ethene, low alkyl group by the vinylbenzene replaced form. Two functional vinyl aromatic monomers such as divinylbenzene can also to exist on a small quantity. Two-(with higher) functional monomers can be used for preparation and are cross-linked and star polymer, and can 5% using at the most with polymer composition. In one embodiment, polymkeric substance is not containing (or substantially not containing) polyfunctional vinyl aromatic monomer.
Embedding section of APIB can depolymerization completely, simultaneously imparting B block oil soluble. B block PVA can give lubricant formulations shear stability, good low-temperature performance and thickening and the depolymerization completely of desirable ground. Therefore, the embedding section of A being present in multipolymer and the amount of B block can reduce based on the needs of lubricating fluid. Preferably the mol ratio of embedding section of A/ (embedding section of A+B) is 0.5-0.97, but can also be 0.7-0.95, or 0.75-0.9.As used herein, phrase " mol ratio of embedding section of A/ (embedding section of A+B) " means the ratio of mole number divided by the repeating unit sum in (embedding section of A+ B block) of the repeating unit in embedding section of A.
In each embodiment of the present invention, the structure of block polymer can be linear, branching or star, and embedding section can with rule, without rule, sequentially, alternation or alternating sequence arrangement. Segmented copolymer can be two embedding sections of AB multipolymers, or three embedding sections of ABA or BAB multipolymers. In one embodiment, multipolymer can be linear programming multipolymer. In another embodiment, multipolymer can be two block sequence segmented copolymers or biblock star type multipolymer. As used herein, term " Sequential block copolymers " means the multipolymer being made up of discrete embedding section (A and B), and described embedding section is separately homogeneous phase, is namely made up of single monomer. The example of Sequential block copolymers comprises those of A-B or B-A-B structure.
In some embodiments, embedding section of PIB of the present invention can comprise a small amount of diene. About the content of embedding section of A in multipolymer, diene content to be less than 10 moles of %, or can be less than 5 moles of %, or is less than 2 moles of % existence. Suitable diene comprises such as 1,4-divinyl or isoprene. In some embodiments, embedding section of A substantially can not contain or even completely contain diene. As used herein, term " substantially not containing diene " means polymkeric substance and contains not more than foreign matter content, and what be generally polymkeric substance is less than 1 mole of %, or the 0.05 of polymkeric substance mole of % or less, or the 0.01 of polymkeric substance mole of % or less, or the diene derived units of the 0 of polymkeric substance mole of %. When segmented copolymer comprises diene, diene can be branching or linear, and multipolymer thinks hydrogenation or unhydrogenated.
In one embodiment; can by the vi-ny l aromatic monomers of the isobutylene monomer of embedding section of A and B block or both be with group; comprise acyl group or halogen-, alkoxyl group-, carboxyl-, hydroxyl-, alkylsulfonyl-, nitro-, nitroso-group-and hydrocarbyl substituent functionalized, wherein alkyl has 1-12 carbon atom usually.
In another embodiment, can by the vi-ny l aromatic monomers of the isobutylene monomer of embedding section of A and B block or both be with ethylenic unsaturated acyl agent grafting. Grafting is by by the vinyl halocarbon (such as bromination) on PVA-PIB skeleton, then the vinyl carbon of halogenation and carboxylic acid or its derivative is made to react in the presence of an activator and carry out, such as what the people such as such as WO/2011/005739, Price disclosed in 13 days January in 2011 instructed.
Can by functionalized further to acylated polymer amine or polyamines. In one embodiment, due to carbon formation control or fuel economy, amine comprises aromatic amine. In one embodiment, being formed and/or sludge conditioning due to acceptable carbon, amine can be aliphatic amine.
The weight-average molecular weight of multipolymer can be 1000-1,000,000, or 5,000-500,000, or 10,000-250,000, or 50,000-175,000. In different embodiments, the polymolecularity of multipolymer is generally 1 to being less than 1.6, or 1-1.55, or 1-1.4, or 1.01-1.2.
Present copolymer can be prepared in any manner known to those skilled in the art. Such as, such as such as PrinciplesofPolymerization, GeorgeOdian, the 3rd edition, the 356th page of living cationic polymerization instructed can provide the vinyl-arene derived units obtaining having relatively high amount relative to other method such as the quick of the product of vinylbenzene and can customize route.Another technology that new sense is introduced method in embedding section of PIB to controllably can be provided can be ATRP polymerization, such as such as HandbookofRadicalPolymerization, KrzysztofMatyjaszewski edits, instructing for 523rd page, ATRP polymerization can provide the multipolymer of the vinyl-arene derived units with relatively low amount. Contriver finds to prepare PIB-PVA segmented copolymer with the use of different methods, can control the PVA content of multipolymer, thus provides the segmented copolymer with differentiation resolution.
There is the oil of lubricant viscosity
Composition comprises the oil with lubricant viscosity. This kind of oil comprises natural and synthetic oil, oil derived from hydrocracking, hydrogenation and hydrofining, non-refining, refining and refining oil and mixture thereof again.
Non-refining oil is usually without (or through little) purification processes further, directly obtain by natural or synthesis source those. Refining oil is similar to non-refining oil, the difference is that they being processed to improve one or more performances further in one or more purification step. Purification techniques is as known in the art, comprises solvent extraction, second distillation, acid or alkali extraction, filtration, diafiltration etc.
Refining oil is also referred to as regeneration or reprocessed oils again, by be similar to the method for obtaining refining oil and obtain and usually additionally by the technology processing being intended to remove useless additive and oil decomposition product.
Animal oil, vegetables oil (such as Viscotrol C, lard), mineral lubricating oils is comprised such as the solvent process of liquid petroleum or paraffinic hydrocarbons, naphthenic hydrocarbon or combination chain alkane-naphthenic type or acid-treated mineral lubricating oils for the preparation of the natural oil of lubricant of the present invention, with the oil derived from coal or shale, or its mixture.
Ucon oil is useful, comprises hydrocarbon ils, such as polymerization and copolyolefine (such as polybutene, polypropylene, propylene isobutylene copolymers); Poly-(the own alkene of 1-), poly-(1-octene), poly-(1-decene) and mixture thereof; Alkylbenzene (such as dodecylbenzene, Tetradecylbenzene, dinonyl benzene, two-(2-ethylhexyl) benzene); Polyphenyl (such as biphenyl, terphenyl, alkylated polyphenyls); Alkylated dipheny ethers and alkylated diphenyl sulfides and derivative, analogue and homologue or its mixture.
Other ucon oil comprises the liquid ester (such as the diethyl ester of Tritolyl Phosphate, trioctyl phosphate and decane phosphonic acids) of phosphoric acid, and polytetrahydrofuran. Synthetic oil is prepared by fischer-tropsch reaction, can be F-T synthesis hydrocarbon or the wax of hydroisomerization usually. In one embodiment, oil is by the preparation of Fischer-Tropsch natural gas synthetic oil (gas-to-liquid) synthesis program and other natural gas synthetic oil.
The oil with lubricant viscosity also can define as described in AmericanPetroleumInstitute (API) BaseOilInterchangeabilityGuidelines. Five groups of base oil are as follows: group I (sulphur content>0.03 weight %, and/or<90 weight % saturatess, viscosity index 80-120); Group II (sulphur content≤0.03 weight %, and>=90 weight % saturatess, viscosity index 80-120); Group III (sulphur content≤0.03 weight %, and>=90 weight % saturatess, viscosity index>=120); Group IV (all polyalphaolefins (PAO)); With group V (all other base oil not included in group I, II, III or IV). The oil with lubricant viscosity comprises API group I, group II, group III, group IV, group V oil or its mixture.Usually, the oil with lubricant viscosity is API group I, group II, group III, group IV oil or its mixture. Or, the oil with lubricant viscosity is generally API group I, group II, group III oil or its mixture.
Lubricant compositions can be enriched material and/or the form preparing lubricant completely. If polymkeric substance of the present invention is the form (it can be combined to form all or part of final lubricant with other oil) of enriched material, then polymkeric substance with there is the oil of lubricant viscosity and/or the weight ratio with thinning oil is 1:99-99:1, or 80:20-10:90.
Other performance additive
Composition optionally comprises other performance additive. Other performance additive comprises following at least one: metal passivator, conventional purification agent (purification agent prepared by means known in the art), dispersion agent, viscosity modifier, friction improver, anti-wear agent, corrosion inhibitor, dispersant viscosity modifiers, extreme pressure agent, wear-resistant liniment, antioxidant, suds suppressor, demulsifying compound, pour point reducer, sealing swelling agent and mixture thereof. Usually, prepare lubricating oil completely containing one or more these performance additive.
Dispersion agent
Dispersion agent commonly known as ashless type dispersants because before being mixed in lubricating oil composition, they do not contain into ash metal and when adding in lubricant and polymeric dispersant they usually can not contribute any become grey metal. Ashless type dispersants is characterised in that the polar group by being connected on hydrocarbon with higher molecular weight chain. Typical ashless dispersant comprises the long-chain alkenyl succinimide that N-replaces. It is 350-5000 that the example of the long-chain alkenyl succinimide that N-replaces comprises the number-average molecular weight of PIB substituting group, or the PIB succinimide of 500-3000. Succinimide dispersants and their preparation method are such as disclosed in United States Patent (USP) 4,234,435. Succinimide dispersants is generally by polyamines, the imide that usually poly-(vinyl-amine) or aromatic polyamine is formed such as aminodiphenylamine (ADPA).
In one embodiment, the present invention also comprises at least one PIB succinimide dispersants, and described dispersion agent is 350-5000 derived from number-average molecular weight, or the PIB of 500-3000. PIB succinimide can combinationally use separately or with other dispersion agent.
In one embodiment, the present invention also comprises at least one derived from PIB succinyl oxide, amine and zinc oxide to form the dispersion agent of the PIB succinimide title complex with zinc. Can be used alone or in combination with the PIB succinimide title complex of zinc.
Another class ashless dispersant is Mannich base. Mannich dispersant is alkylphenol and the reaction product of aldehyde (especially formaldehyde) and amine (especially polyalkylene polyamine). Alkyl is usually containing at least 30 carbon atoms.
Also can by dispersion agent by ordinary method by with plurality of reagents in any one reaction and aftertreatment. Wherein, these be boron, urea, thiocarbamide, dimercaptothiodiazole, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, hydrocarbon replace succinyl oxide, maleic anhydride, nitrile, epoxide, phosphorus compound and/or metallic compound.
Dispersion agent can with the 0-20 weight % of lubricating composition, or 0.1-15 weight %, or 0.1-10 weight %, or 1-6 weight %, or 7-12 weight % exists.
Purification agent
Lubricant compositions optionally also comprises other known neutrality or high alkaline detergent. Suitable purification agent matrix comprise phenates, containing thiophenol salt, sulfonate, salixarate, salicylate, carboxylic acid, phosphoric acid, list-and/or phosphorodithioic acid, alkylphenol, sulphur coupling alkylphenol compound, or saligenin.Various high alkaline detergent and their preparation method are described in greater detail in a large amount of patent publications, comprise in WO2004/096957 and the reference wherein quoted.
Purification agent can with 0-10 weight %, or 0.1-8 weight %, or 1-4 weight %, or is greater than 4 to 8 weight % and exists.
Antioxidant
Anti-oxidant compounds is known, comprises such as olefine sulfide, diarylamine, hindered phenol, molybdenum compound (such as molybdenum dithiocarbamate) and mixture thereof. Anti-oxidant compounds can be used alone or combinationally uses. Antioxidant can with the 0-20 weight % of lubricating composition, or 0.1-10 weight %, or 1-5 weight %, and 1.5-3.0 weight % exists in some cases.
Hindered phenol antioxidant usually containing sec-butyl and/or the tertiary butyl as space steric hindrance group. Phenolic group can be replaced by alkyl and/or the bridge linkage group that is connected on the 2nd aryl further. The example of suitable hindered phenol antioxidant comprises 2,6 di t butyl phenol, 4-methyl-2,6 di t butyl phenol, 4-ethyl-2,6-DI-tert-butylphenol compounds, 4-propyl group-2,6-DI-tert-butylphenol compounds or 4-butyl-2,6 di t butyl phenol or 4-dodecyl-2,6 di t butyl phenol. In one embodiment, hindered phenol antioxidant can be ester, can comprise such as from the Irganox of CibaTML-135. Suitable finds containing being described in more detail in United States Patent (USP) 6,559,105 of ester hindered phenol antioxidant chemistry.
Diarylamine antioxidant can contain one or more nitrogen-atoms. Aryl can between two nitrogen-atoms or nitrogen-atoms can have two and connect aryl thereon. In diarylamine antioxidant, the substituting group of aryl can comprise aliphatic hydrocarbyl as having the alkyl of 1-30 carbon atom, hydroxyl, halogen group, carboxylic acid or ester group or nitro. Preferred aryl groups can be substituted or unsubstituted phenyl or naphthyl. One or two aryl can be replaced, such as monoalkylation pentanoic, dialkylated diphenylamine, or single-and the mixture of two-alkylated diphenylamine. The suitable example of the diarylamine that can use includes but not limited to pentanoic and alkylated diphenylamine, nonox and alkylation phenyl-naphthylamines and mixture thereof.
Can be used as the suitable example of the molybdenum dithiocarbamate of antioxidant to comprise with trade(brand)name such as Molyvan822TMAnd MolyvanTMA is by R.T.VanderbiltCo., Ltd. with AdekaSakura-LubeTMThe commercial materials that S-100, S-165 and S-600 are sold by AsahiDenkaKogyoK.K and mixture thereof.
Viscosity modifier
Although polymkeric substance of the present invention can be used as viscosity modifier, it is possible to there is other viscosity modifier of other type. This kind of viscosity modifier is the material known, comprise the ester of the styrene butadiene rubbers of hydrogenation, ethylene-propylene copolymer, the styrene-isoprene polymkeric substance of hydrogenation, the isoprene copolymer of hydrogenation, poly-(methyl) acrylate (usual polyalkyl methacrylate), polyoxyethylene alkylphenyl ethene, polyolefine and maleic anhydride-styrene copolymers, or its mixture. Other viscosity modifier this kind of can with the 0-15 weight % of lubricating composition, or 0.1-10 weight %, or 1-5 weight %, or 0.5-2 weight % exists in some cases.
Anti-wear agent
Lubricant compositions optionally also comprises other anti-wear agent of at least one. Anti-wear agent can with the 0-15 weight % of lubricating composition, or 0.1-10 weight % or 1-8 weight %, or 0.5-2 weight % exists in some cases.The example of suitable anti-wear agent comprises phosphoric acid ester; olefine sulfide; containing the ashless wear preventive additive of sulphur; for metal dialkyl dithiophosphate (such as zinc dialkyl dithiophosphate); containing the compound of thiocarbamate, the thiocarbamate of such as thiocarbamate, thiocarbamate acid amides, thiocarbamate ether, alkylidene group coupling and two (S-alkyl dithio carbamyl) disulphide.
Compound containing dithiocarbamate is prepared by making dithiocarbamic acid or salt and unsaturated compound reaction. Compound containing dithiocarbamate is also prepared by making amine, dithiocarbonic anhydride and unsaturated compound simultaneous reactions. Generally speaking, reaction carries out at the temperature of 25-125 DEG C. United States Patent (USP) 4,758,362 and 4,997,969 describes dithio carbamate compounds and its preparation method.
Sulfuration can comprise propylene, butylene, iso-butylene, amylene, hexane, heptene, octane, nonene, decene, undecylene, dodecylene, undecyl, 13 carbenes, 14 carbenes, 15 carbenes, cetene, heptadecene, octadecylene, 18 carbenes, 19 carbenes, eicosylene or its mixture to form the example of the suitable alkene of olefine sulfide. In one embodiment, cetene, heptadecene, octadecylene, 18 carbenes, 19 carbenes, eicosylene or its mixture and their dipolymer, trimer and tetramer are especially useful alkene. Or, alkene can be that diene is if 1,3-divinyl and unsaturated ester are such as Er Siaerde (Diesl-Alder) affixture of butyl acrylate.
Another class olefine sulfide comprises lipid acid and their ester. Lipid acid is obtained by vegetables oil or animal oil usually, usually containing 4-22 carbon atom. The example of suitable fat acid and their ester comprises triglyceride level, oleic acid, linolic acid, Zoomeric acid or its mixture. Usually, lipid acid is obtained by lard, Yatall MA, peanut oil, soya-bean oil, oleum gossypii seminis, sunflower seed oil or its mixture. In one embodiment, by lipid acid and/or ester and olefin.
In optional embodiment, ash-free antiwear agent can be polyvalent alcohol and aliphatic carboxylic acid, usually contains the monoesters of the acid of 12-24 carbon atom. Usually, the monoesters of polyvalent alcohol and aliphatic carboxylic acid is the form of the mixture with sunflower oil etc., and it can with the 5-95 of described mixture, or 10-90 in other embodiments, or 20-85, or 20-80 weight % is present in friction modifier mixture. The aliphatic carboxylic acid (especially monocarboxylic acid) forming ester is those acid usually containing 12-24 or 14-20 carbon atom. The example of carboxylic acid comprises dodecylic acid, stearic acid, lauric acid, mountain acid and oleic acid.
Polyvalent alcohol comprises dibasic alcohol, three ethanol and has the alcohol of the alcohol class OH group of higher number. Polyvalent alcohol comprises ethylene glycol, comprises glycol ether, triglycol and Tetraglycol 99; Propylene glycol, comprises dipropylene glycol, tripropylene glycol and four propylene glycol; Glycerine; Butyleneglycol; Hexylene glycol; Sorbitol Powder; Arabitol; Mannitol; Sucrose; Fructose; Glucose; Cyclohexanediol; Tetrahydroxybutane; And tetramethylolmethane, comprise Dipentaerythritol and tripentaerythritol. Usually, polyvalent alcohol is glycol ether, triglycol, glycerine, Sorbitol Powder, tetramethylolmethane or Dipentaerythritol.
It is called that the commercially available monoesters of " XU 61518.10 " is considered to comprise 60 ± 5 weight % chemical species XU 61518.10, and 35 ± 5% glyceryl dioleate and be less than 5% trioleate and oleic acid.The amount of above-mentioned monoesters is calculated based on the actual correction gauge of the polyol monoesters existed in any this kind of mixture.
Anti scuffing agent
Lubricant compositions also can comprise anti scuffing agent. think that the anti scuffing immunomodulator compounds reducing adhesion wear is generally sulfocompound. usually, sulfocompound includes machine sulfide and polysulphide, such as benzyldithio toluene, two (chlorine benzyl) two sulfur vulcanization thing, dibutyl tetrasulfide, two-tertiary butyl polysulphide, the sulfuration methyl esters of oleic acid, sulphurized alkyl phenols, sulfuration limonene, sulfuration terpenes, this Alder adduct of sulfuration Deere, alkyl sulfenyl N ' N-dialkyl dithio amino formate, the reaction product of polyamines and polybasic ester, 2, the isobutyric chlorine of 3-dibromo propoxy is for fourth ester, the acetoxymethyl of dialkyldithiocarbamacompositions and the acyloxyalkyi ethers of xanthogenic acid and mixture thereof.
Extreme pressure agent
The extreme pressure agent (EP) dissolved in oil comprises the EP agent containing sulphur and chloride sulphur, chlorinated hydrocarbon EP agent and phosphorus EP agent. The example of this kind of EP agent comprises chlorinated wax; Organic sulfide and polysulphide, the such as Witconol 2301 of benzyl disulfide compound, two-(chlorine benzyl) disulphide, dibutyl tetrasulfide, sulfuration, sulfenyl phenolate, sulfuration limonene, sulfuration terpenes and sulfuration Er Si alder adducts; Phosphosulfurized hydrocarbon, the such as reaction product of sulfuration phosphorus and turps or Witconol 2301; Phosphorus ester, such as two hydrocarbon and three hydrocarbon phosphorous acid esters, such as dibutyl phosphite, phosphorous acid two ester in heptan, phosphorous acid two cyclohexyl, phosphorous acid amyl group phenyl ester; The phenol phosphorous acid ester that phosphorous acid diamyl phenyl ester, phosphorous acid tridecyl ester, phosphorous acid two stearyl and polypropylene replace; Metal thiocarbamate, such as dioctyl zinc dithiocarbamate and heptylphenol diacid barium; The zinc salt of phosphorodithioic acid; The amine salt of alkyl and Acidic phosphates, comprises the amine salt of the reaction product of such as dialkyl dithiophosphoric acid and propylene oxide; And mixture.
Other additive
Other performance additive as corrosion inhibitor comprise described in U. S. application US05/038319 (on October 25th, 2004 submit to, specify contriver McAtee and Boyer) 5-8 section those, octylame octylate, dodecenyl succinic acid or acid anhydride and lipid acid is such as the condensation product of oleic acid and polyamines. In one embodiment, corrosion inhibitor comprisesCorrosion inhibitor. Synalox corrosion inhibitor is generally homopolymer or the multipolymer of propylene oxide.Corrosion inhibitor is described in greater detail in the product manual FormNo.118-01453-0702AMS that DowChemicalCompany publishes. This product manual title is " SYNALOXLubricants, High-PerformancePolyglycolsforDemandingApplications ".
Metal passivator, comprises the derivative of benzotriazole, dimercaptothiodiazole derivative, 1,2,4-triazole, benzoglyoxaline, 2-alkyl dithio benzoglyoxaline or 2-alkyl dithio benzothiazole; Suds suppressor, comprises ethyl propenoate and the multipolymer of 2-EHA and optional vinyl-acetic ester; Demulsifying compound, comprises trialkylphosphate, polyoxyethylene glycol, polyoxyethylene, polyoxytrimethylene and (ethylene oxide-propylene oxide) polymkeric substance; Pour point reducer, comprises the ester of maleic anhydride-styrene, polymethacrylate, polyacrylic ester or polyacrylamide; And friction improver, comprising fatty alkyl component, such as derivative of fatty acid, the amine salt of the such as condensation product of amine, ester, epoxide, fatty imidazolines, carboxylic acid and polyalkylene polyamine, and alkylphosphonic acid carboxylic acid also can be used in lubricant compositions.Fatty alkyl means C usually10-C22Alkyl, it typically is straight chain and optionally unsaturated. Friction improver can exist with the 0-10 weight % of lubricating composition or 0.1-8 weight % or 1-5 weight %.
Industrial application
Present copolymer is suitable for any lubricant compositions. Polymkeric substance can be used as viscosity modifier and/or dispersant viscosity modifiers (being commonly referred to DVM).
In one embodiment, polymkeric substance of the present invention provides following at least one performance: acceptable viscosity modified performance, acceptable dispersing agent performance and acceptable coke build-up and sludge conditioning. When polymkeric substance of the present invention is used in engine oil lubricants composition, its provides acceptable fuel economy performance or acceptable coke build-up and sludge conditioning usually further.
The example of lubricant comprises the engine oil for 2 strokes or 4 stroke IC engines, gear oil, automatic transmission fluid, hydraulic fluid, turbine oil, metal working fluids or turning oil.
In one embodiment, oil engine can be diesel combustion engine, gasoline combustion engine, combustion of natural gas engine or blend gasoline/alcohol combustion engine. In one embodiment, oil engine is diesel combustion engine, in another embodiment, is gasoline combustion engine.
Oil engine can be 2 strokes or 4 two-stroke engines. Suitable oil engine comprises marine diesel, aviation piston engine, underload diesel engine, and automobile and truck engine.
Any engine lubricant can be suitable for and no matter sulphur, phosphorus or vitriol ash (ASTMD-874) content for the lubricant compositions of oil engine. The sulphur content of engine oil lubricants can be 0.01-1 weight %, or 0.01-0.8 weight %, or 0.01-0.5 weight %, or 0.01-0.3 weight %. Equally, engine oil can not have any sulphur content. The phosphorus content of engine oil can be 0.01-0.2 weight %, or 0.01-0.1 weight %, or 0.01-0.085 weight %, or even 0.01-0.06 weight %, or 0.01-0.055 weight %, or 0.01-0.05 weight %. Equally, engine oil can not comprise any phosphorus. Total vitriol ash content can be 0.01-2 weight %, or 0.01-1.5 weight %, or 0.01-1.1 weight %, or 0.01-1 weight %, or 0.01-0.8 weight %, or 0.01-0.5 weight %. Equally, engine oil can be free of, or substantially not containing any vitriol ash content.
In one embodiment, lubricating composition is engine oil, wherein lubricating composition has (i) 0.5 weight % or less sulphur content, (ii) 0.1 weight % or less phosphorus content, and (iii) 1.5 weight % or less vitriol ash content.
In one embodiment, lubricating composition is suitable for 2 strokes or 4 stroke marine diesel oil oil engines. In one embodiment, marine diesel oil combustion engine is 2 two-stroke engines. Can by polymkeric substance of the present invention with 0.01-20 weight %, or 0.05-10 weight %, or 0.1-5 weight % adds in marine diesel oil lubricating composition.
In several embodiments, suitable lubricating composition comprises based on the additive that active substance exists with scope shown in table 1a and 1b.
Table 1a
Table 1b
Following examples provide the elaboration to the present invention. These embodiments are not detailed and are not intended to limit the content of the present invention.
Embodiment
Embodiment 1-living cationic polymerization
PS-PIB multipolymer according to reaction formula below by living cationic polymerization with cumyl chlorine initiator and TiCl4Prepared by promotor.Gained multipolymer has the polymolecularity of about 19.4 moles of % vinylbenzene and 80.6 moles of % iso-butylenes, the Mw of 13900, the Mn of 11200 and 1.23.
Embodiment 2ATRP polymerization
PS-PIB multipolymer changes into ATRP macromole evocating agent according to signal formula below by hydroboration, finally changes into vinylbenzene-b-iso-butylene and prepares by high vinylidene 5000MnPIB. Gained multipolymer has about 4.7 moles of % vinylbenzene and 95.3 moles of % iso-butylenes, Mw of the 10600 and Mn of 8600.
Embodiment 3Thermogravimetric analysis (TGA)
For determining the type of the thermolysis of PS-PIB multipolymer, speed and degree, use TGA with relative to PIB (Mw37,000, about 40-50% hyperergy PIB), styrene butadiene rubbers (SBR) (Mw130,000, about 29 moles of % vinylbenzene) and OCP (Mw130,000) sample, contrast product prepared by the method according to embodiment 1 and 2.
Method: (1) thermolysis Hi.Res.Sensitivity1.0 in nitrogen, rise with 10 DEG C/min, reach 5-550 DEG C, switch to air, rise with 10 DEG C/min, reach 5-600 DEG C, (2) at 285 DEG C constant temperature so that 30 DEG C/min to rise to 285 DEG C, switch to air, constant temperature 1440 minutes.
Result: (1), based on the temperature (table 1) when retaining 1-4% polymkeric substance, two kinds of PS-PIB products (grade 2 and 3) all demonstrate the performance close to PIB (grade 1). Two kinds of PS-PIB multipolymers all than OCP (grade 5) and SBR (grade 4) perform well many. PS-PIB (grade 2) by the synthesis of ATRP route is than the multipolymer (grade 3) synthesized by living cationic polymerization better executive. Based on inorganic residues (table 2), present copolymer is rated 2 and be listed as 4. Usual known PIB decomposes completely, speculates that the relatively low-styrene-content of ATRP multipolymer is and the reason of active cation performance of copolymer difference.
(2) isothermal experiment is designed to simulate the behavior of the polymkeric substance when the 2nd piston ring rib (landring) temperature of turbo-charging direct oil injection type (TDI) engine. As seen in table 3, best executive is also PIB, thereafter closely be two kinds of present copolymer. Relatively the ATRP multipolymer of low-styrene-content is also the better executive of specific activity cationic copolymer.
As used in this specification, term " hydrocarbyl substituent " or " alkyl " use with its conventional meaning well known to those skilled in the art. Specifically, it refers to the group that has the carbon atom being connected directly between on molecule rest part and mainly have hydrocarbon character. The example of alkyl comprises:
(i) hydrocarbon substituent, i.e. aliphatic series (such as alkyl or alkenyl), Zhi Huan race (such as cycloalkyl, cycloalkenyl group) substituting group, with aromatics-, the aromatic substituent that replaces of aliphatic series-and Zhi Huan race, and wherein ring completes the cyclic substituents of (such as two substituting groups form ring together) by another part of this molecule;
(ii) hydrocarbon substituent replaced, namely contains the substituting group of the non-hydrocarbyl group (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfinyl) of the main hydrocarbon character not changing substituting group in the context of the present invention;
(iii) assorted substituting group, namely in the context of the present invention, containing the substituting group being different from carbon in the ring being made up of carbon atom or chain while having main hydrocarbon character. Heteroatoms comprises sulphur, oxygen and nitrogen, and comprises substituting group such as pyridyl, furyl, thienyl and imidazolyl. Generally speaking, for every 10 carbon atoms, exist not more than 2 in alkyl, it is preferable that not more than 1 non-hydrocarbon substituent;Usually, alkyl does not exist non-hydrocarbon substituent.
More known above-mentioned materialss may interact in final preparaton so that the component of final preparaton may from originally add those are different. The product thus formed, comprises the product through being formed so that its intended use uses lubricant compositions of the present invention and may be not easy to describe. But, all this kind of improvement and reaction product include within the scope of the invention; The present invention comprises the lubricant compositions by said components mixing being prepared.
By reference each file mentioned above is attached to herein. Except in embodiment or except clearly illustrating in addition, all quantity describing the amount of material, reaction conditions, molecular weight, carbonatoms etc. in this manual are to be understood that is modified by wording " about ". Unless otherwise explanation, each chemical mentioned herein or composition should be understood to the commercial grade material that can contain isomer, by product, derivative and usually be to be understood that other this kind of material being present in commercial grade. But, unless otherwise explanation, the scale of each chemical composition is illustrated as eliminating any solvent or thinning oil that usually can be present in commercial materials. It is to be understood that the upper limit and the lower limit of amount described herein, scope and ratio can independently combine. Similarly, the scope of each element of the present invention can use with amount together with the scope of other element any or amount.
Although explaining the present invention about preferred embodiment, it should be understood that through reading this specification sheets, its each improvement can be understood by those skilled in the art. Thus, it is to be understood that invention disclosed herein is intended to contain this kind of improvement belonging in scope.
Claims (16)
1. a lubricating composition, it comprises: the oil with lubricant viscosity, with the segmented copolymer comprising at least one poly-(iso-butylene) (PIB) polymer blocks (embedding section of A) and at least one poly-(vinyl-arene) (PVA) polymer blocks (B block), wherein the mol ratio of embedding section of A/ (embedding section of A+B) is 0.7-0.95, and the weight ratio of segmented copolymer and the oil with lubricant viscosity is 1:99-99:1.
2. composition according to claim 1, wherein PVA is poly-(vinylbenzene) (PS).
3. composition according to claim 1, wherein the mol ratio of embedding section of A/ (embedding section of A+B) is 0.96.
4. composition according to claim 1, wherein the mol ratio of embedding section of A/ (embedding section of A+B) is 0.80.
5. composition according to claim 1, wherein embedding section of A comprises the diene derived units being less than 10 moles of %.
6. lubricating composition according to claim 1, wherein segmented copolymer is prepared by living cationic polymerization.
7. lubricating composition according to claim 1, wherein segmented copolymer is the mixture of the segmented copolymer prepared by living cationic polymerization and ATRP polymerization.
8. lubricating composition according to claim 1, wherein segmented copolymer is prepared by ATRP polymerization.
9. lubricating composition according to claim 1, wherein multipolymer has the number-average molecular weight of 1000-1,000,000.
10. lubricating composition according to claim 9, wherein multipolymer has the number-average molecular weight of 10,000-250,000.
11. lubricating compositions according to claim 1, wherein hydrogenated copolymer has 1 to the polymolecularity being less than 1.6.
12. lubricating compositions according to claim 11, wherein hydrogenated copolymer has the polymolecularity of 1.01-1.4.
13. lubricating compositions according to claim 1, wherein multipolymer is Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.
14. lubricating compositions according to claim 1, wherein multipolymer is Sequential block copolymers.
15. 1 kinds control the sedimental method in lubricant compositions, it comprises the segmented copolymer adding in lubricant compositions and comprising at least one PIB polymer blocks (embedding section of A) and at least one PVA polymer blocks (B block), wherein the mol ratio of embedding section of A/ (embedding section of A+B) is 0.7-0.95, and the weight ratio of the oil with lubricant viscosity that segmented copolymer and lubricant compositions comprise is 1:99-99:1.
16. methods according to claim 15, wherein PVA polymkeric substance is poly-(vinylbenzene).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161489305P | 2011-05-24 | 2011-05-24 | |
| US61/489,305 | 2011-05-24 | ||
| PCT/US2012/038750 WO2012162207A1 (en) | 2011-05-24 | 2012-05-21 | Lubricating composition comprising poly (isobutylene) /poly (vinyl aromatic) block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103717719A CN103717719A (en) | 2014-04-09 |
| CN103717719B true CN103717719B (en) | 2016-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280036305.7A Expired - Fee Related CN103717719B (en) | 2011-05-24 | 2012-05-21 | Comprise the lubricating composition of poly-(iso-butylene)/poly-(vinyl-arene) segmented copolymer |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9428709B2 (en) |
| EP (1) | EP2714870A1 (en) |
| JP (1) | JP5917685B2 (en) |
| CN (1) | CN103717719B (en) |
| CA (1) | CA2837056A1 (en) |
| WO (1) | WO2012162207A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019040576A1 (en) * | 2017-08-25 | 2019-02-28 | Exxonmobil Research And Engineering Company | Ashless engine lubricants for high temperature applications |
| US11326004B2 (en) * | 2017-10-14 | 2022-05-10 | Tpc Group Llc | Isobutylene copolymers, method for making isobutylene copolymers and isobutylene copolymer products |
| WO2020126494A1 (en) | 2018-12-19 | 2020-06-25 | Evonik Operations Gmbh | Use of associative triblockcopolymers as viscosity index improvers |
| US11697782B2 (en) * | 2020-07-09 | 2023-07-11 | ExxonMobil Technology and Engineering Company | Engine oil lubricant compositions and methods for making same with superior engine wear protection and corrosion protection |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992310A (en) * | 1971-11-16 | 1976-11-16 | The British Petroleum Company Limited | Copolymers |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976607A (en) | 1968-05-10 | 1976-08-24 | Velsicol Chemical Corporation | Copolymers and preparational method therefor |
| US3948868A (en) | 1969-04-03 | 1976-04-06 | Exxon Research And Engineering Company | Homogeneous styrene/isoolefin copolymers |
| GB1360689A (en) * | 1971-11-16 | 1974-07-17 | British Petroleum Co | Polystyrene/polyisobutylene vi improver |
| US3994993A (en) | 1975-06-19 | 1976-11-30 | The Firestone Tire & Rubber Company | Diblock copolymers and process of preparing same |
| US4234435A (en) | 1979-02-23 | 1980-11-18 | The Lubrizol Corporation | Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation |
| US4758362A (en) | 1986-03-18 | 1988-07-19 | The Lubrizol Corporation | Carbamate additives for low phosphorus or phosphorus free lubricating compositions |
| US4997969A (en) | 1988-12-12 | 1991-03-05 | The Lubrizol Corporation | Carbamate additives for lubricating compositions |
| US5038319A (en) | 1989-04-24 | 1991-08-06 | Xerox Corporation | System for recording and remotely accessing operating data in a reproduction machine |
| US5458796A (en) * | 1994-03-31 | 1995-10-17 | Shell Oil Company | Synthesis of polyisobutylene star-branched polymers via living carbocationic polymerization |
| US7056983B2 (en) * | 1998-04-28 | 2006-06-06 | Kaneka Corporation | Block copolymer |
| US6265486B1 (en) | 1998-12-31 | 2001-07-24 | Exxon Mobil Chemical Patents Inc. | Triblock copolymers incorporating a styrene/isoolefin copolymer midblock |
| US6228945B1 (en) * | 1999-12-20 | 2001-05-08 | The University Of Akron | Three arm star compositions of matter having diblock arms based on polyisobutylene and methods of preparation |
| US6559105B2 (en) | 2000-04-03 | 2003-05-06 | The Lubrizol Corporation | Lubricant compositions containing ester-substituted hindered phenol antioxidants |
| WO2004096957A1 (en) | 2003-04-24 | 2004-11-11 | The Lubrizol Corporation | Diesel lubricant low in sulfur and phosphorus |
| EP2001983B1 (en) * | 2006-03-27 | 2015-02-18 | The Lubrizol Corporation | Lubricating compositions containing a styrene-butadiene diblock copolymer |
| WO2007136700A2 (en) * | 2006-05-17 | 2007-11-29 | The University Of Akron | Method of purifying block copolymers |
| JP5203590B2 (en) | 2006-10-27 | 2013-06-05 | 出光興産株式会社 | Lubricating oil composition |
| CA2767802A1 (en) | 2009-07-08 | 2011-01-13 | The Lubrizol Corporation | Dispersant viscosity modifiers |
| JP2012219243A (en) * | 2011-04-13 | 2012-11-12 | Kaneka Corp | Viscosity index improver for lubricating oil, and liquid lubricating oil composition |
-
2012
- 2012-05-21 US US14/118,359 patent/US9428709B2/en active Active
- 2012-05-21 CA CA2837056A patent/CA2837056A1/en not_active Abandoned
- 2012-05-21 EP EP12724054.7A patent/EP2714870A1/en not_active Ceased
- 2012-05-21 JP JP2014512908A patent/JP5917685B2/en not_active Expired - Fee Related
- 2012-05-21 CN CN201280036305.7A patent/CN103717719B/en not_active Expired - Fee Related
- 2012-05-21 WO PCT/US2012/038750 patent/WO2012162207A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992310A (en) * | 1971-11-16 | 1976-11-16 | The British Petroleum Company Limited | Copolymers |
Also Published As
| Publication number | Publication date |
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| WO2012162207A1 (en) | 2012-11-29 |
| CA2837056A1 (en) | 2012-11-29 |
| EP2714870A1 (en) | 2014-04-09 |
| JP2014517865A (en) | 2014-07-24 |
| US20140274850A1 (en) | 2014-09-18 |
| JP5917685B2 (en) | 2016-05-18 |
| US9428709B2 (en) | 2016-08-30 |
| CN103717719A (en) | 2014-04-09 |
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